Selective production of linear tetraethylenepentamine and hydroxyethyldiethylenetriamine

ABSTRACT

This invention relates to a process for making amines having a high yield weight percent of linear tetraethylenepentamine (L-TEPA) and hydroxyethyldiethylenetriamine (HEDETA) by condensing an amino compound in the presence of a condensation catalyst selected from a Group IVB metal oxide, a Group VIB metal-containing substance and a promoted condensation catalyst. This invention also relates to an alkyleneamines producers composition rich in L-TEPA and HEDETA.

RELATED APPLICATIONS

The following are related, commonly assigned applications, filed on an even date herewith; U.S. patent application Ser. No. 501,917. U.S. patent application Ser. No. 501,919; U.S. patent application Ser. No. 501,906; U.S. patent application Ser. No. 501,907; U.S. patent application Ser. No. 501,998; U.S. patent application Ser. No. 501,826; and U.S. patent application Ser. No. 501,920; all incorporated herein by reference.

The following are related, commonly assigned applications: U.S. patent application Ser. No. 07/136,615, filed Dec. 22, 1987; U.S. patent application Ser. No. 07/390,829, filed Aug. 8, 1989; U.S. patent application Ser. No. 07/390,706, filed Aug. 8, 1989; U.S. patent application Ser. No. 07/390,709, filed Aug. 8, 1989 (now U.S. Pat. No. 4,983,736); U.S. patent application Ser. No. 07/390,828, filed Aug, 8 1989 (now U.S. Pat. No. 5,101,074); U.S. patent application Ser. No. 07/390,708, filed Aug. 8, 1989 now abandoned in favor of continuation Ser. No. 07/742,731, filed Aug. 16, 1991, which in turn has been abandoned in favor of continuation Ser. No. 934,901, filed Aug. 26, 1992); and U.S. patent application Ser. No. 07/390,714, filed Aug. 8, 1989; all incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION

1. Technical Field

This invention relates to a process for making amines having a high yield weight percent of linear tetraethylenepentamine (L-TEPA) and hydroxyethyldiethylenetriamine (HEDETA) by condensing an amino compound in the presence of a condensation catalyst selected from a Group IVB metal oxide, a Group VIB metal-containing substance and a promoted condensation catalyst.

This invention also relates to an alkyleneamines producers composition rich in L-TEPA and HEDETA.

2. Background of the Invention

There is a substantial body of literature directed to the use of various acid catalysts to effect intramolecular and intermolecular condensation of amino compounds. U.S. Pat. No. 2,073,671 and U.S. Pat. No. 2,467,205 constitute early prior work on the use of acid condensation catalysts to condense amino compounds. U.S. Pat. No. 2,073,671 discusses, in a general fashion, the catalytic intermolecular condensation of alcohols and amines or ammonia using the same phosphate catalysts later favored by U.S. Pat. No. 2,467,205 for the intramolecular condensation of amines. The two patents are not in harmony over the use of other materials as catalysts. To illustrate this point, U.S. Pat. No. 2,073,671 states:

"Alumina, thoria, blue oxide of tungsten, titania, chromic oxide, blue oxide of molybdenum and zirconia have been mentioned in the literature for use as catalysts in carrying out these reactions but their effectiveness is so low that no practical application has been made of their use."

whereas U.S. Pat. No. 2,467,205 in describing the self-condensation of ethylenediamine (EDA) under vapor phase conditions, to initially produce ethyleneamines, but after recycle, eventually generates piperazine (PIP) through multistep condensation reactions, followed by deamination, recommends "dehydration catalysts" which are thereafter characterized as

"silica gel, titania gel, alumina, thoria, boron phosphate, aluminum phosphate, and the like."

U.S. Pat. No 2,073,671 describes the condensation catalyst in the following terms:

" . . . a heated catalyst or contact mass containing phosphorus and especially one or more of the oxygen acids of phosphorus, their anhydrides, their polymers, and their salts; for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous pentoxide, dimetaphosphoric acid, trimetaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, normal ammonium phosphate, ammonium metaphosphate, secondary ammonium pyrophosphate, normal ammonium pyrophosphate, aluminum phosphate, aluminum acid phosphate and mixtures of two or more of such materials."

whereas U.S. Pat. No. 2,467,205 describes one of the preferred catalysts as "basic aluminum phosphate".

U.S. Pat. No. 2,454,404 describes the "catalytic deamination of alkylene polyamines" by reacting DETA vapor over solid catalysts such as activated alumina, bauxite, certain aluminum silicates such as kaolin and oxides of thorium, titanium and zirconium.

U.S. Pat. Nos. 2,073,671 and 2,467,205 demonstrate a common experience in using aluminum phosphate as a condensation catalyst to produce aliphatic amines, and U.S. Pat. Nos. 2,454,404 and 2,467,205 contemplate the other solid catalysts for deamination of amines to make heterocyclic noncyclic amines. In general, the reaction conditions under which deamination to effect cyclization occurs are more severe than those employed for condensation to generate noncyclic molecules, all other factors being comparable.

U.S. Pat. Nos. 4,540,822, 4,584,406 and 4,588,842 depict the use of Group IVB metal oxides as supports for phosphorus catalysts used to effect the condensation of amino compounds with alkanolamines.

U.S. Pat. No. 4,683,335 describes the use of tungstophosphoric acid, molybdophosphoric acid or mixtures deposited on titania as catalysts for the condensation of amines and alkanolamines to make polyalkylenepolyamines.

U.S. Pat. Nos. 4,314,083, 4,316,840, 4,362,886 and 4,394,524 disclose the use of certain metal sulfates as useful catalysts for the condensation of alkanolamine and an amino compound. No distinction is made between the sulfur compounds in respect to catalytic efficacy. Sulfuric acid is as good as any metal sulfate, and all metal sulfates are treated as equivalents. At column 8 of U.S. Pat. No. 4,314,083, it is noted that boron sulfate "gave extremely high selectivity at a low level" of EDA. However, selectivity in general was shown to increase with an increase of EDA relative to monoethanolamine (MEA) in the feed. The only specific metal sulfates disclosed in the patents are antimony sulfate, beryllium sulfate, iron sulfate and aluminum sulfate.

In the typical case of the manufacture of alkyleneamines, mixtures with other alkyleneamines (including a variety of polyalkylenepolyamines and cyclic alkylenepolyamines) are formed. The same holds true when the object of the process is to produce polyalkylenepolyamines whether acyclic or cyclic, in that a variety of amino compounds are also formed. Each of these cyclic and acyclic alkyleneamines can be isolated from the mixture.

The acid catalyzed condensation reaction involving the reaction of an alkanolamine with an amino compound in the presence of an acidic catalyst is believed to proceed through the mechanism of esterifying free surface hydroxyl groups on the acid catalyst with the alkanolamine and/or by protonating the alkanolamine in the presence of the acid catalyst, followed by loss of water and amine condensation of the ester or the hydrated species, as the case may be, to form the alkyleneamine. Illustrative prior art directed primarily to the cyclic polyalkylenepolyamines (heterocyclic polyamines), but not necessarily limited to the aforementioned acid condensation reaction, are: U.S. Pat. Nos. 2,937,176, 2,977,363, 2,977,364, 2,985,658, 3,056,788, 3,231,573, 3,167,555, 3,242,183, 3,297,701, 3,172,891, 3,369,019, 3,342,820, 3,956,329, 4,017,494, 4,092,316, 4,182,864, 4,405,784 and 4,514,567; European Patent Applications 0 069 322, 0 111 928 and 0 158 319; East German Patent No. 206,896; Japanese Patent Publication No. 51-141895; and French Patent No. 1,381,243. The evolution of the art to the use of the acid catalyzed condensation reaction to generate acyclic alkyleneamines, particularly acyclic polyalkylenepolyamines, as the predominant products stemmed from the initial disclosure in U.S. Pat. No. 4,036,881, though earlier patent literature fairly well characterized such as effect without labeling it so, see U.S. Pat. No. 2,467,205, supra. The acid catalysts are phosphorus compounds and the reaction is carried out in the liquid phase. The trend in this catalyst direction was early set as demonstrated by U.S. Pat. Nos. 2,073,671 and 2,467,205, supra. A modification of this route includes the addition of ammonia to the reaction, see, for example, U.S. Pat. No. 4,394,524 and U.S. Pat. No. 4,463,193 for the purpose of converting alkanolamine such as MEA in situ to alkylene amine such as EDA by reaction with ammonia, and the EDA is in situ reacted with MEA according to the process of U.S. Pat. No. 4,036,881 to form alkyleneamines.

A summary of the prior art employing said catalysts for making alkyleneamines is set forth in Table I below:

                                      TABLE I                                      __________________________________________________________________________     CITATION    CATALYST TYPE    REACTANTS                                         __________________________________________________________________________     U.S. Pat. No. 2,467,205                                                                    Silica gel, titania gel, alumina,                                                               Vapor phase condensation of                                   thoria, aluminum phosphate.                                                                     EDA over a fixed bed of the                                   Preferred catalyst is basic                                                                     catalyst, multipass process                                   aluminum phosphate.                                                                             shifts from polyethylene-                                                      polyamines with the first few                                                  cycles.                                           U.S. Pat. No. 4,036,881                                                                    Phosphorus containing substances                                                                Alkanolamine and alkylene-                                    selected from the group consisting                                                              amine in liquid phase                                         of acidic metal phosphates,                                                                     reaction.                                                     phosphoric acid compounds and                                                  their anhydrides, phosphorus acid                                              compounds and their anhydrides,                                                alkyl or aryl phosphate esters,                                                alkyl or aryl phosphite esters,                                                alkyl or aryl substituted                                                      phosphorous and phosphoric acids                                               wherein said alkyl groups have                                                 from 1 to about 8 carbon atoms and                                             said aryl groups have from 6 to                                                about 20 carbon atoms, alkali                                                  metal monosalts of phosphoric                                                  acid, the thioanalogs of the fore-                                             going, and mixtures of the above.                                  U.S. Pat. No. 4,044,053                                                                    Phosphorus containing substances                                                                Alkanepolyols and alkylene-                                   selected from the group consisting                                                              amine in liquid phase                                         of acidic metal phosphates,                                                                     reaction.                                                     phosphoric acid compounds and                                                  their anhydrides, phosphorus                                                   acid compounds and their                                                       anhydrides, alkyl or aryl                                                      phosphate esters, alkyl or aryl                                                phosphite esters, alkyl or aryl                                                substituted phosphorous acids and                                              phosphoric acids wherein said                                                  alkyl groups have from 1 to about                                              8 carbon atoms and said aryl                                                   groups have from 6 to about 20                                                 carbon atoms, alkali metal mono-                                               salts of phosphoric acid and                                                   mixtures of the above.                                             U.S. Pat. No. 4,314,083                                                                    Salt of a nitrogen or sulfur con-                                                               Alkanolamine and an                                           taining substance or the corres-                                                                alkyleneamine in liquid                                       ponding acid.    phase reaction.                                   U.S. Pat. No. 4,316,840                                                                    Metal nitrates and sulfates                                                                     Reforming linear polyamines.                                  including zirconium sulfate.                                       U.S. Pat. No. 4,316,841                                                                    Phosphate, preferably boron                                                                     Reforming linear polyamines.                                  phosphate.                                                         U.S. Pat. No. 4,324,917                                                                    Phosphorous-containing cation                                                                   Alkanolamine and an alkylene-                                 exchange resin.  amine in liquid phase                                                          reaction.                                         U.S. Pat. No. 4,362,886                                                                    Arsenic, antimony or bismuth                                                                    Alkanolamine and an alkylene-                                 containing compounds. Antimony                                                                  amine in liquid phase                                         sulfate specifically disclosed.                                                                 reaction.                                         U.S. Pat. No. 4,399,308                                                                    Lewis acid halide.                                                                              Alkanolamine and an alkylene-                                                  amine in liquid phase                                                          reaction.                                         U.S. Pat. No. 4,394,524                                                                    Phosphorus-containing substance                                                                 Ammonia, alkanolamine and an                                  or salt of a sulfur-containing                                                                  alkyleneamine in liquid phase                                 substance, or the corresponding                                                                 reaction.                                                     acid.                                                              U.S. Pat. No. 4,448,997                                                                    Reacts alumina with phosphoric                                                                  EDA with MEA.                                                 acid, adds ammonium hydroxide.                                     U.S. Pat. No. 4,463,193                                                                    Group IIIB metal acid phosphate.                                                                Ammonia, alkanolamine and                                                      an alkyleneamine.                                 U.S. Pat. No. 4,503,253                                                                    Supported phosphoric acid.                                                                      Ammonia, alkanolamine and                                                      an alkyleneamine.                                 U.S. Pat. No. 4,521,600                                                                    Select hydrogen phosphates and                                                                  Alkanolamine and an alkylene-                                 pyrophosphates.  amine.                                            U.S. Pat. No. 4,524,143                                                                    Phosphorus impregnated onto                                                                     Alkanolamine and an alkylene-                                 zirconium silicate suport.                                                                      amine.                                            U.S. Pat. No. 4,540,822                                                                    Phosphorus compound deposited                                                                   Alkanolamine and an alkylene-                                 on a Group IVB metal oxide                                                                      amine, regenerates the                                        support.         catalyst with O.sub.2 -containing                                              gas.                                              U.S. Pat. No. 4,547,591                                                                    Silica-alumina alone or in                                                                      An ethyleneamine and an                                       combination with an acidic                                                                      alkanolamine; ethyleneamines;                                 phosphorus cocatalyst.                                                                          or ammonia and an alkanol-                                                     amine.                                            U.S. Pat. No. 4,550,209                                                                    An intercalatively catalytically                                                                EDA and MEA.                                                  active tetravalent zirconium                                                   polymeric reaction product of an                                               organo phosphonic acid or an                                                   ester thereof with a compound of                                               tetravalent zirconium reactive                                                 therewith.                                                         U.S. Pat. No. 4,552,961                                                                    Phosphorus amide compound.                                                                      Alkyleneamine and alkanolamine                                                 and/or alkylene glycol.                           U.S. Pat. No. 4,555,582                                                                    Phosphorus chemically bonded to                                                                 MEA and EDA.                                                  a zirconium silicate support.                                      U.S. Pat. No. 4,560,798                                                                    Rare earth metal or strontium                                                                   MEA.                                                          acid phosphate.                                                    U.S. Pat. No. 4,578,517                                                                    Group IIIB metal acid phosphate.                                                                Ammonia or p-/s-amine                                                          and alkanolamine.                                 U.S. Pat. No. 4,578,518                                                                    Thermally activated, calcined,                                                                  MEA and EDA.                                                  pelleted titania containing                                                    titanium triphosphate. " . . . the                                             titania that was used was . . .                                                anatase." (Col. 9, lines 18-19).                                   U.S. Pat. No. 4,578,519                                                                    Thermally activated, calcined,                                                                  MEA and EDA with optional                                     pelleted titania with chemically                                                                recycle of DETA.                                              bonded phosphorus derived from                                                 polyphosphoric acid.                                               U.S. Pat. No. 4,584,405                                                                    Activated carbon, optionally                                                                    MEA and EDA.                                                  treated to incorporate phosphorus.                                             Activated carbon may be washed                                                 with strong mineral acid to                                                    remove impurities followed by                                                  water wash. Optional treatment                                                 follows.                                                           U.S. Pat. No. 4,584,406                                                                    Pelleted Group IVB metal oxide                                                                  MEA and EDA.                                                  with chemically bonded phosphorus                                              derived from phosphoryl chloride                                               or bromide.                                                        U.S. Pat. No. 4,588,842                                                                    Thermally activated pelleted                                                                    MEA and EDA.                                                  Group IVB metal oxide with                                                     chemically bonded phosphorus.                                      U.S. Pat. No. 4,605,770                                                                    Group IIA or IIIB metal acid                                                                    Alkanolamine and an                                           phosphate.       alkyleneamine "in liquid                                                       phase".                                           U.S. Pat. No. 4,609,761                                                                    Thermally activated pelleted                                                                    MEA and EDA.                                                  titania with chemically bonded                                                 phosphorus.                                                        U.S. Pat. No. 4,612,397                                                                    Thermally activated pelleted                                                                    MEA and EDA.                                                  titania with chemically bonded                                                 phosphorus.                                                        U.S. Pat. No. 4,617,418                                                                    Acid catalysts, mentions "beryl-                                                                Ammonia, alkanolamine and                                     lium sulfate".   an alkyleneamine "under                                                        vapor phase conditions".                          Japanese Patent                                                                            Variety of phosphorus and metal                                                                 Ammonia, alkanolamine and                         Application phosphates including Group IVB                                                                  ethyleneamine, with ammonia/                      #1983 - 185,871,                                                                           phosphates.      alkanolamine molar ratio                          Publication                  greater than 11.                                  #1985 - 78,945                                                                 U.S. Pat. No. 4,683,335                                                                    Tungstophosphoric acid, molybdo-                                                                Claims reaction of MEA and                                    phosphoric acid or mixtures                                                                     EDA, but discloses self-                                      deposited on titania. Examples                                                                  condensation reaction of                                      2-7 characterize titania surface                                                                EDA and DETA.                                                 areas of 51, 60 and 120 m.sup.2 /gm.                               Japanese Patent                                                                            Group IVB metal oxide with                                                                      Ammonia and MEA.                                  Application bonded phosphorus.                                                 #1985 - 078,391,                                                               Publication                                                                    #1986 -236,752                                                                 Japanese Patent                                                                            Group IVB metal oxide with                                                                      Ammonia and MEA.                                  Application bonded phosphorus.                                                 #1985 - 078,392,                                                               Publication                                                                    #1986 -236,753                                                                 U.S. Pat. No. 4,698,427                                                                    Titania having phosphorus                                                                       Diethanolamine and/or                                         thermally chemically bonded                                                                     hydroxyethyldiethylene-                                       to the surface thereof in the                                                                   triamine in EDA.                                              form of phosphate bonds.                                           U.S. Pat. No. 4,806,517                                                                    Pelleted Group IVB metal oxide                                                                  MEA and EDA.                                                  with phosphorus thermally                                                      chemically bonded to the                                                       surface thereof.                                                   European Patent                                                                            Titania and zirconia chemically                                                                 MEA and EDA.                                      Application bonded to phosphorus.                                              331,396                                                                        __________________________________________________________________________

A summary of additional prior art for making alkyleneamines is set forth in Table II below.

                                      TABLE II                                     __________________________________________________________________________     CITATION CATALYST TYPE    REACTANTS                                            __________________________________________________________________________     Japanese Patent                                                                         Niobium-containing                                                                              Ammonia, alkyleneamine and                           Application                                                                             substance.       alkylene glycol.                                     #1987 - 312,182,                                                               Publication                                                                    #1989 - 153,659                                                                Japanese Patent                                                                         Niobium-containing                                                                              Ammonia, alkyleneamine                               Application                                                                             substance added  and alkanolamine.                                    #1987 - 325,274,                                                                        to water-containing liquid.                                           Publication                                                                    #1989 - 168,647                                                                Japanese Patent                                                                         Niobium oxide    Ammonia, alkyleneamine                               Application                                                                             obtained from    and alkanolamine                                     #1987 - 321,348,                                                                        niobium alkoxide.                                                     Publication                                                                    #1989 - 163,159                                                                Japanese Patent                                                                         Niobium pentoxide                                                                               Ammonia, alkyleneamine                               Application               and dialkanolamine.                                  #1987 - 314,132,                                                               Publication                                                                    #1989 - 157,936                                                                Japanese Patent                                                                         Niobium-containing                                                                              Ammonia, alkyleneamine                               Application                                                                             substance.       and alkanolamine.                                    #1987 - 290,652,                                                               Publication                                                                    #1989 - 132,550                                                                Japanese Patent                                                                         Tantalum-containing                                                                             Ammonia, alkyleneamine                               Application                                                                             substance.       and alkanolamine.                                    #1987 - 142,284,                                                               Publication                                                                    #1989 - 307,846                                                                European Patent                                                                         Mixed oxide      Ammonia, alkyleneamine                               Application                                                                             containing niobium                                                                              and alkanolamine.                                    315,189  oxide.                                                                European Patent                                                                         Niobium-containing                                                                              Ammonia, alkyleneamine                               Application                                                                             substance supported                                                                             and alkanolamine.                                    328,101  on a carrier.                                                         Japanese Patent                                                                         Titania and zirconia                                                                            MEA and EDA.                                         Application                                                                             chemically bonded with                                                #1989 - 048,699,                                                                        phosphorus in the form                                                Publication                                                                             of a hydroxy-containing                                               #1990 - 006,854                                                                         phosphate group.                                                      Japanese Patent                                                                         Niobium oxide and titania,                                                                      Ammonia, alkyleneamine                               Application                                                                             alumina, silica or zirconia.                                                                    and alkanolamine.                                    #1988 - 262,861,                                                               Publication                                                                    #1990 - 002,876                                                                Japanese Patent                                                                         Niobium oxide treated with                                                                      Ammonia, alkyleneamine                               Application                                                                             an acid.         and alkanolamine.                                    #1988 - 290,106,                                                               Publication                                                                    #1990 - 000,735                                                                Japanese Patent                                                                         Niobium-containing                                                                              Ammonia, alkyleneamine                               Application                                                                             substance on a carrier.                                                                         and alkanolamine.                                    #1988 - 027,489,                                                               Publication                                                                    #1990 - 000,736                                                                Japanese Patent                                                                         Three constituent catalyst-                                                                     Alcohol or aldehyde and                              Application                                                                             copper; one or more elements                                                                    ammonia, a primary                                   #1988 - 261,366,                                                                        selected from chromium,                                                                         amine or a secondary amine.                          Publication                                                                             manganese, iron and zinc;                                             #1990 - 000,232                                                                         and a platinum group element.                                         Japanese Patent                                                                         Four constituent catalyst-copper;                                                               Alcohol or aldehyde                                  Application                                                                             one or more elements selected                                                                   and ammonia, a primary                               #1988 - 261,368,                                                                        from chromium, manganese, iron,                                                                 amine or a secondary amine.                          Publication                                                                             cobalt, nickel and zinc;                                              #1990 - 000,233                                                                         a platinum group element; and                                                  one or more elements selected                                                  from lithium, sodium, potassium,                                               rubidium, cesium, magnesium,                                                   calcium, strontium and barium.                                        Japanese Patent                                                                         Four constituent catalyst-copper;                                                               Alcohol or aldehyde and                              Application                                                                             one or more elements selected from                                                              ammonia, a primary amine                             #1988 - 261,369,                                                                        chromium, manganese, iron, cobalt,                                                              or a secondary amine.                                Publication                                                                             nickel and zinc; a platinum group                                     #1990 - 000,234                                                                         element; and one or more elements                                              selected from aluminum, tungsten                                               and molybdenum.                                                       __________________________________________________________________________

A market demand for L-TEPA and HEDETA has been progressively developing in recent years. It would be desirable to satisfy this developing demand from a cost standpoint by modifying slightly the commercial processes directed to the manufacture of polyalkylene polyamines from suitable starting raw materials to the production of L-TEPA and HEDETA as major products.

It would be desirable to have continuously produced compositions, generated by the reaction of diethanolamine (DEA) and EDA or other suitable starting raw materials over a fixed bed of a condensation catalyst under commercial conditions, that are rich in L-TEPA and HEDETA and that are not disproportionately high in AEP and other cyclics.

The above features are provided by this invention.

SUMMARY OF THE INVENTION

This invention relates in general to a process of making amines having a high yield weight percent of L-TEPA and HEDETA which comprises condensing an amino compound in the presence of a condensation catalyst selected from a Group IVB metal oxide, a Group VIB metal-containing substance and a promoted condensation catalyst. The amino compound used herein preferably comprises an alkyleneamine and a dialkanolamine, in particular, EDA and DEA. The condensation catalysts used herein contain sufficient residual bound hydroxyl groups or other groupings which renders catalyst formation possible by loss of water or its chemical equivalent such as ammonium hydroxide.

More particularly, this invention relates to a process of making amines having a high yield weight percent of L-TEPA and HEDETA by the (i) intramolecular condensation of an amino compound to an amine having a lower molecular weight or (ii) the intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcoholic hydroxyl group using a particularly defined condensation catalyst. The process of this invention primarily involves intermolecular condensation reactions. A preferred process involves the manufacture of L-TEPA and HEDETA by an intermolecular condensation reaction utilizing EDA and DEA as reactants and a Group VIB metal-containing substance or a Group IVB metal oxide as the condensation catalyst.

The invention further relates to a continuously generated alkyleneamines producers composition comprising, based on 100 percent of the weight of the composition and exclusive of any water and/or ammonia and/or feed present,

a) greater than about 8.0 weight percent of L-TEPA,

b) greater than about 10.0 weight percent of HEDETA,

c) less than about 30.0 weight percent of AEP,

d) less than about 35.0 weight percent of others,

e) a HEDETA to L-TEPA weight ratio of less than about 10.0, and

f) a L-TEPA+HEDETA to AEP weight ratio of greater than about 2.0.

As used herein, the term "amino compound" embraces ammonia and any compound containing nitrogen to which is bonded an active hydrogen. Also, as used herein, the term "oxide" embraces oxides, hydroxides and/or mixtures thereof. Further, as used herein, the term "others" embraces polyalkylene polyamines, byproducts and the like.

For purpose of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover. Also, for purposes of this invention, Group IIIB metal oxides embraces the lanthanides and actinides.

DETAILED DESCRIPTION

L-TEPA and HEDETA are very useful commercial products for a variety of applications including fuel oil additives, corrosion inhibitors, fabric softners, epoxy curing agents and others. There is a developing need for the ability to commercially generate larger production quantities of L-TEPA and HEDETA and that is the direction of this invention. The process of this invention provides for the reaction of DEA and EDA or other suitable starting raw materials to produce in a continuous manner a reaction product mixture, termed herein an "alkyleneamines producers composition", in which L-TEPA and HEDETA are principal products of the reaction.

The process of this invention is distinctive insofar as it achieves the generation of high concentrations of L-TEPA and HEDETA in a manner which can be suitably employed in a commercial process, particularly a continuous process, for the manufacture of alkyleneamines. In particular, the process of this invention allows the production of L-TEPA and HEDETA in relatively high yields without generating large amounts of cyclic alkyleneamine products.

As indicated above, this invention relates to a process of making amines having a high yield weight percent of L-TEPA and HEDETA which comprises condensing an amino compound in the presence of a catalytically effective amount of a condensation catalyst selected from a Group IVB metal oxide, a Group VIB metal-containing substance and a promoted condensation catalyst. The amino compound preferably comprises an alkyleneamine and a dialkanolamine, in particular, EDA and DEA.

As also indicated above, this invention relates to a continuously generated alkyleneamines producers composition comprising, based on 100 percent of the weight of the composition and exclusive of any water and/or ammonia and/or feed present,

a) greater than about 8.0 weight percent of L-TEPA,

b) greater than about 10.0 weight percent of HEDETA,

c) less than about 30.0 weight percent of AEP,

d) less than about 35.0 weight percent of others,

e) a HEDETA to L-TEPA weight ratio of less than about 10.0, and

f) a L-TEPA+HEDETA to AEP weight ratio of greater than about 2.0.

The alkyleneamines producers composition of this invention can be subjected to conventional separations techniques for recovering the individual components of the composition. Such techniques are well known in the art and include, for example, distillation.

This invention contemplates the catalyzed condensation by (i) intramolecular condensation of an amino compound to an amine having a lower molecular weight, and (ii) intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcohol hydroxyl group to an amine having a lower, same or higher molecular weight than the reactants, in the presence of a particularly defined condensation catalyst. The process of this invention primarily involves intermolecular condensation reactions.

A wide variety of condensation catalysts can be used in this invention. Illustrative of suitable condensation catalysts for use in this invention include, for example, Group IVB metal oxides, Group VIB metal-containing substances and promoted condensation catalysts.

The Group IVB metal oxide condensation catalysts are preferred catalysts for use in this invention. Suitable Group IVB metal oxide condensation catalysts are disclosed in U.S. patent application Ser. No. 07/390,829, filed Aug. 8, 1989 and incorporated herein by reference. Illustrative of Group IVB metal oxide condensation catalysts include, for example, titanium oxide and zirconium oxide, preferably titanium dioxide and zirconium dioxide including mixtures thereof.

The Group VIB metal-containing condensation catalysts are also preferred catalysts for use in this invention. Suitable Group VIB metal-containing condensation catalysts are disclosed in the above-cited related U.S. patent application Ser. No. 07/390,708, Aug. 8, 1989 and incorporated herein by reference. Illustrative of Group VIB metal-containing condensation catalysts include, for example, one or more oxides of tungsten, chromium, molybdenum or mixtures thereof.

A variety of promoted condensation catalysts are also desirable for use in this invention. Suitable promoted condensation catalysts are disclosed in U.S. patent application Ser. No. 07/390,714, filed Aug. 8, 1989 and incorporated herein by reference. The condensation catalysts are promoted by a condensation catalyst promoter as described hereinafter. Illustrative of such condensation catalysts include, for example, one or more Group IVB metal oxides and Group VIB metal-containing substances.

The condensation catalyst promoter for use in this invention should be capable of promoting the condensation catalyst. The promoting effect can relate to catalytic activity, product selectivity and/or catalyst stability (mechanical or dimensional strength of the catalyst). Illustrative of condensation catalyst promoters for use in this invention can include, for example, one or more metal oxides, one or more metallic phosphates which may or may not have a cyclic structure, one or more metallic polyphosphates having a condensed structure, one or more Group VIB metal-containing substances and one or more conventional materials such as mineral acids or compounds derived from mineral acids. Mixtures of condensation catalyst promoters may also be employed in this invention. For purposes of this invention, the condensation catalyst promoter should be different from the condensation catalyst; however, the condensaton catalyst promoter and the performance moderator described hereinafter can be the same or different.

This invention also embraces the use of vicinal di(hetero)alkylene organometalates in the selective preparation of L-TEPA and HEDETA. Suitable vicinal di(hetero)alkylene organometalates are disclosed in U.S. patent application Ser. No. 07/390,828, filed Aug. 8, 1989 and incorporated herein by reference.

The level of activity of the condensation catalysts of the invention is that level which of itself makes the catalysts at least as active in the condensation of amines as, for example, is phosphoric acid on an equivalent basis. Preferably, the condensation catalysts on a support should have a surface area greater than about 20 m² /gm to as high as about 260 m² /gm or greater depending upon which metal oxide described below that is employed. In the case of titanium oxides, the surface area should be greater than about 140 m² /gm to as high as about 260 m² /gm, more preferably, greater than about 160 m² /gm to as high as about 260 m² /gm, determined according to the single point N₂ method. In the case of zirconia oxides, the surface area should be greater than about 70 m² /gm to as high as about 150 m² /gm, more preferably, greater than about 90 m² /gm to as high as about 135 m² /gm, determined according to the single point N₂ method. It is appreciated that the performance moderators described below which can be used in association with the condensation catalyst and the condensation catalyst promoters described above can affect the surface area of the condensation catalyst. While surface areas described above may be preferred, for purposes of this invention, the surface area of the condensation catalyst should be sufficient to contribute to product selectivity, catalytic activity and/or mechanical or dimensional strength of the catalyst.

Though the condensation catalyst of the invention provides sufficient activity to effect the condensation reaction, certain combinations of reactants and/or product formation can be benefited by treating the catalyst with a catalyst moderator, hereinafter termed a "performance moderator". Performance moderators are widely used to promote the performance of catalysts in areas of selectivity to certain products and the repression of a catalyst's proclivity to generate a broad range of reaction products. A range of suitable materials may impact the condensation catalysts of this invention in the variety of reaction products. The performance moderator may be any material which impacts the condensation catalyst's selection of reaction products or which changes the proportion of any one or more of the reaction products which the condensation catalyst generates at comparable processing conditions. In addition to contributing to product selectivity, the performance moderator may be any material which contributes to catalytic activity and/or catalyst stability (mechanical or dimensional strength).

Illustrative performance moderators for use in this invention can include, for example, one or more metal oxides, one or more metallic phosphates which may or may not have a cyclic structure, one or more metallic polyphosphates having a condensed structure, one or more Group VIB metal-containing substances and one or more conventional materials such as mineral acids or compounds derived from mineral acids. Mixtures of performance moderators may also be employed in this invention. For purposes of this invention, the performance moderator should be different from the condensation catalyst; however, the performance moderator and the condensation catalyst promoter can be the same or different.

Illustrative of metal oxides which may be utilized as performance moderators in association with the condensation catalyst include, for example, one or more of the following: Group IA metal oxides, Group IIA metal oxides, Group IIIB metal oxides (including lanthanides and actinides), Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIB metal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VA metal oxides, Group VIA metal oxides and Group IVB metal oxides or mixtures thereof. Certain of these metal oxides may also be used as condensation catalysts in accordance with this invention such as Group IVA and IVB metal oxides. Preferred metal oxides are amphoteric or slightly acidic or slightly basic. Preferred metal oxides which may be utilized in association with the condensation catalyst include, for example, one or more oxides of beryllium, scandium, yttrium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, tungsten, iron, cobalt, zinc, silver, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony and bismuth.

Group IVB metal oxides such as titanium dioxide and zirconium dioxide and Group IVA metal oxides such as silica and germania are preferred for use in this invention. For mixed metal oxides in which at least one of the metals is titanium, suitable metals in association with titanium may include, for example, one or more of the following: Group IIIB metals such as scandium, yttrium and lanthanum including the lanthanides, Group VB metals such as niobium and tantalum, Group VIB metals such as chromium, molybdenum and tungsten, Group VIII metals such as iron, cobalt and nickel, Group IIB metals such as zinc and cadmium, Group IIIA metals such as boron, aluminum, gallium and indium, Group IVA metals such as silicon, germanium, tin and lead, Group VA metals such as arsenic, antimony and bismuth, and Group IVB metals such as zirconium and hafnium. For mixed metal oxides in which at least one of the metals is zirconium, suitable metals in association with zirconium may include, for example, one or more of the following: Group IVA metals such as silicon, germanium, tin and lead, Group VB metals such as niobium and tantalum, and Group VIB metals such as chromium, molybdenum and tungsten. Certain of these metal oxides may also be effective as condensation catalysts for use in this invention.

Illustrative of mixed metal oxides which may be used as performance moderators in association with the condensation catalyst include, for example, TiO₂ --SiO₂, TiO₂ --Al₂ O₃, TiO₂ --CdO, TiO₂ --Bi₂ O₃, TiO₂ --Sb₂ O₅, TiO₂ --SnO₂, TiO₂ --ZrO₂, TiO₂ --BeO, TiO₂ --MgO, TiO₂ --CaO, TiO₂ --SrO, TiO₂ --ZnO, TiO₂ --Ga₂ O₃, TiO₂ --Y₂ O₃, TiO₂ --La₂ O₃, TiO₂ --MoO₃, TiO₂ --Mn₂ O₃, TiO₂ --Fe₂ O₃, TiO₂ --Co₃ O₄, TiO₂ --WO₃, TiO₂ --V₂ O₅, TiO₂ --Cr₂ O₃, TiO₂ --ThO₂, TiO₂ --Na₂ O, TiO₂ --BaO, TiO₂ --CaO, TiO₂ --HfO₂, TiO₂ --Li₂ O, TiO₂ --Nb₂ O₅, TiO₂ --Ta₂ O₅, TiO₂ --Gd₂ O₃, TiO₂ --Lu₂ O₃, TiO₂ --Yb₂ O₃, TiO₂ --CeO₂, TiO₂ --Sc₂ O₃, TiO₂ --PbO, TiO₂ --NiO, TiO₂ --CuO, TiO₂ --CoO, TiO₂ --B₂ O₃, ZrO₂ --SiO₂, ZrO₂ --Al₂ O₃, ZrO₂ --SnO, ZrO₂ --PbO, ZrO₂ --Nb₂ O₅, ZrO₂ --Ta₂ O₅, ZrO₂ --Cr₂ O₃, ZrO₂ --MoO₃, ZrO₂ --WO₃, ZrO₂ --TiO₂, ZrO₂ --HfO₂, TiO₂ --SiO₂ --Al₂ O₃, TiO₂ --SiO₂ --ZnO, TiO₂ --SiO₂ --ZrO₂, TiO₂ --SiO₂ --CuO, TiO₂ --SiO₂ --MgO, TiO₂ --SiO₂ --Fe₂ O₃, TiO₂ --SiO₂ --B₂ O₃, TiO₂ --SiO₂ --WO₃, TiO₂ --SiO₂ --Na₂ O, TiO₂ --SiO₂ --MgO, TiO₂ --SiO₂ --La₂ O₃, TiO₂ --SiO₂ --Nb₂ O₅, TiO₂ --SiO₂ --Mn₂ O₃, TiO₂ --SiO₂ --Co₃ O₄, TiO₂ --SiO₂ --NiO, TiO₂ --SiO₂ --PbO, TiO₂ --SiO₂ --Bi₂ O₃, TiO₂ --Al₂ O₃ --ZnO, TiO₂ --Al₂ O₃ --ZrO₂, TiO₂ --Al₂ O₃ --Fe₂ O₃, TiO₂ --Al₂ O₃ --WO₃, TiO₂ --Al₂ O₃ --La₂ O₃, TiO₂ --Al₂ O₃ --Co₃ O₄, ZrO₂ --SiO₂ --Al₂ O₃, ZrO₂ --SiO₂ --SnO, ZrO₂ --SiO₂ --Nb₂ O₅, ZrO₂ --SiO₂ --WO₃, ZrO₂ --SiO₂ --TiO₂, ZrO₂ --SiO₂ --MoO₃, ZrO₂ --SiO₂ --HfO₂, ZrO₂ --SiO₂ --Ta₂ O₅, ZrO₂ --Al₂ O₃ --SiO₂, ZrO₂ --Al₂ O₃ --PbO, ZrO₂ --Al₂ O₃ --Nb₂ O₅, ZrO₂ --Al₂ O₃ --WO₃, ZrO₂ --Al₂ O₃ --TiO₂, ZrO₂ --Al₂ O₃ --MoO₃, ZrO₂ --HfO₂ --Al₂ O₃, ZrO₂ --HfO₂ --TiO₂, and the like. Other suitable mixed metal oxides embraced within the scope of this invention are disclosed by Tanabe et al., Bulletin of the Chemical Society of Japan, Vol. 47(5), pp. 1064-1066 (1974).

The metal oxides described herein which can be used as performance moderators in association with the condensation catalyst may contribute to product selectivity and/or catalytic activity of the reaction and/or stability of the catalyst. The catalyst structure can comprise from about 0 to about 90 percent or greater by weight of the metal oxide, preferably from about 0 to about 75 percent by weight of the metal oxide, and more preferably from about 0 to about 50 percent by weight of the metal oxide, the remainder being the weight of the condensation catalyst. For mixed metal oxides containing titania, higher concentrations of titania can provide very desirable L-TEPA and HEDETA selectivities. As discussed hereinafter, the condensation catalyst of this invention may also contain support(s), binding agent(s) or other additives to stabilize or otherwise help in the manufacture of the catalyst.

The metallic phosphate and polyphosphate performance moderators may or may not have a cyclic structure and may or may not have a condensed structure. Suitable metallic phosphates having a cyclic structure or an acyclic structure are disclosed in U.S. patent application Ser. No. 07/390,706, filed Aug. 8, 1989 and incorporated herein by reference. Suitable metallic polyphosphates having a condensed structure are disclosed in U.S. patent application Ser. No. 07/390,709 filed Aug. 8, 1989, and incorporated herein by reference (now U.S. Pat. No. 4,983,736). Illustrative of metallic phosphate and polyphosphate performance moderators include, for example, metallic orthophosphates (PO₄ ⁻³), metallic pyrophosphates (P₂ O₇ ⁻⁴), metallic polyphosphates (including tripolyphosphates (P₃ O₁₀ ⁻⁵), tetrapolyphosphates (P₄ O₁₃.sup. -6), pentapolyphosphates (P₅ O₁₆ ⁻⁷) and higher polyphosphates), metallic metaphosphates (including trimetaphosphates (P₃ O₉ ⁻³), tetrametaphosphates (P₄ O₁₂ ⁻⁴) and other lower and higher metaphosphates) and metallic ultraphosphates (condensed phosphates containing more P₂ O₅ than corresponds to the metaphosphate structure). Corresponding metallic metaphosphimates, metallic phosphoramidates and metallic amido- and imidophosphates of the above may also be used as performance moderators in accordance with this invention. Suitable metals which can be incorporated into the metallic phosphate and polyphosphate performance moderators include, for example, Group IA metals, Group IIA metals, Group IIIB metals, Group IVB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIII metals, Group IB metals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VA metals, Group VIA metals and mixtures thereof.

Illustrative of metallic orthophosphates which may be utilized in this invention include, for example, NaH₂ PO₄, KH₂ PO₄, RbH₂ PO₄, LiH₂ PO₄, CsH₂ PO₄, MgHPO₄, CaHPO₄, YPO₄, CePO₄, LaPO₄, ThPO₄, MnPO₄, FePO₄, BPO₄, AlPO₄, BiPO₄, Mg(H₂ PO₄)₂, Ba(H₂ PO₄)₂, Mg(NH₄)₂ PO₄, Ca(H₂ PO₄)₂, La(H₂ PO₄)₃ and the like. Illustrative of metallic pyrophosphates which maybe utilized in this invention include, for example, Na₂ H₂ P₂ O₇, K₂ H₂ P₂ O₇, Ca₂ P₂ O₇, Mg₂ P₂ O₇, KMnP₂ O₇, AgMnP₂ O₇, BaMnP₂ O₇, NaMnP₂ O₇, KCrP₂ O₇, NaCrP₂ O₇, Na₄ P₂ O₇, K₄ P₂ O₇, Na₃ HP₂ O₇, NaH₃ P₂ O₇, SiP₂ O₇, ZrP₂ O₇, Na₆ Fe₂ (P₂ O₇)₃, Na₈ Fe₄ (P₂ O₇)₅, Na₆ Cu(P₂ O₇)₂, Na₃₂ Cu₁₄ (P₂ O₇)₁₅, Na₄ Cu₁₈ (P₂ O₇)₅, Na(NH₄)₂ P₂ O₇, Ca(NH₄)₂ P₂ O₇, MgH₂ P₂ O₇, Mg(NH₄)₂ P₂ O₇) and the like. Illustrative of metallic polyphosphates which may be utilized in this invention include, for example, NaSr₂ P₃ O₁₀, NaCa₂ P₃ O₁₀, NaNi₂ P₃ O₁₀, Na₅ P₃ O₁₀, K₅ P₃ O₁₀, Na₃ MgP₃ O₁₀, Na₃ CuP₃ O₁₀, Cu₅ (P₃ O₁₀)₂, Na₃ ZnP₃ O₁₀, Na₃ CdP₃ O₁₀, Na₆ Pb(P₃ O₁₀)₂, Na₃ CoP₃ O₁₀, K₃ CoP₃ O₁₀, Na₃ NiP₃ O₁₀, K₂ (NH₄)₃ P₃ O₁₀, Ca(NH₄)₂ P₃ O₁₀, La(NH₄)₃ P₃ O₁₀, NaMgH₂ P₃ O₁₀ and the like. Illustrative of metallic metaphosphates which may be utilized in this invention include, for example, Na₃ P₃ O₉, K₃ P₃ O₉, Ag₃ P₃ O₉, Na₄ P₄ O₁₂, K₄ P₄ O₁₂, Na₂ HP₃ O₉, Na₄ Mg(P₃ O₉)₂, NaSrP₃ O₉, NaCaP₃ O₉, NaBaP₃ O₉, KBaP₃ O₉, Ca₃ (P₃ O₉)₂, Ba(P₃ O₉)₂, Na₂ Ni₂ (P₃ O₉)₂, Na₄ Ni(P₃ O₉)₂, Na₄ Co(P₃ O₉)₂, Na₄ Cd(P₃ O₉)₂ and the like. Illustrative of metallic ultraphosphates which may be utilized in this invention include, for example, CaP₄ O₁₁, Ca₂ P₆ O₁₇, Na₈ P₁₀ O₂₉, Na₆ P₈ O₂₃, Na₂ CaP₆ O₁₇, Na₂ P₄ O₁₁, NaBaP₇ O₁₈, Na₂ P₈ O₂₁, K₄ P₆ O₁₇ and the like. The preferred metallic phosphate and polyphosphate performance moderators for use in this invention include Group IA metal dihydrogen orthophosphates, Group IA metal metaphosphates and Group IA metal dihydrogen pyrophosphates, more preferably NaH₂ PO₄, Na₃ P₃ O₉, Na₄ P₄ O₁₂ and Na₂ H₂ P₂ O₇. Other suitable metallic phosphate and polyphosphate performance moderators which are embraced within the scope of this invention are disclosed by Van Wazer, J. R., Phosphorus and Its Compounds, Vol. 1, Interscience Publishers, Inc., New York (1958).

The metallic phosphate and polyphosphate performance moderators can be prepared by conventional methods known in the art. Sodium is believed to be one of a small group of cations effective for stabilizing six-membered cyclic metaphosphates at their temperatures of fusion (about 625° C.) without decomposition to linear and/or other condensed phosphates including mixtures. The formation of cyclic and acyclic metallic phosphate and polyphosphate structures appears to depend on the cation ionic size, the coordination number of the cation and the ionic or covalent nature of the metal-oxygen bond.

While not wishing to be bound to any particular theory, it is believed that those metallic phosphate and polyphosphate performance moderators and promoters encompassed within the scope of this invention having a cyclic structure and possessing ionic character and/or ion exchange capacity contribute to desired activity and product selectivity when used in appropriate amounts as described hereinbelow. While the reaction mixture may initially include one or more metallic phosphates and/or metallic polyphosphates other than metallic phosphates and polyphosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity, it is believed to be desirable that such metallic phosphates and polyphosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity be formed in situ in order to contribute to desired activity and product selectivity. In such instances, the preparation conditions or reaction conditions should allow for the formation of metallic phosphates and polyphosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity. Mixtures of metallic phosphates and polyphosphates having a cyclic structure and possessing ionic character and/or ion exchange capacity with metallic phosphates and polyphosphates having other than a cyclic structure and other than ionic character and/or ion exchange capacity are believed to contribute to desired activity and product selectivity.

Illustrative of Group VIB metal-containing substances which can be utilized as performance moderators in association with the condensation catalyst are described hereinabove. Such Group VIB metal-containing substances can contribute to product selectivity, catalytic activity and/or catalyst stability (mechanical or dimensional strength of the catalyst). Certain of these Group VIB metal-containing substances may also be effective as condensation catalysts for use in this invention.

Illustrative of conventional materials which can be utilized as performance moderators in association with the condensation catalyst include a mineral acid or a compound derived from a mineral acid. Suitable for use as performance moderators are one or more phosphoric acid or a salt of phosphoric acid, hydrogen fluoride, hydrofluoric acid or a fluoride salt, sulfuric acid or a salt of sulfuric acid, and the like. The performance moderator may also be organic esters of phosphoric acid or a salt of phosphoric acid, hydrogen fluoride organic complexes, hydrofluoric acid organic complexes or a fluoride salt organic complexes, organic esters of sulfuric acid or a salt of sulfuric acid, and the like. Suitable salts of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate and the like.

A variety of conventional phosphorus-containing substances may be suitable for use as performance moderators in this invention. The conventional substances should be capable of functioning as a performance moderator. Illustrative of conventional phosphorus-containing substances may include, for example, those disclosed in U.S. Pat. No. 4,036,881, U.S. Pat. No. 4,806,517, U.S. Pat. No. 4,617,418, U.S. Pat. No. 4,720,588, U.S. Pat. No. 4,394,524, U.S. Pat. No. 4,540,822, U.S. Pat. No. 4,588,842, U.S. Pat. No. 4,605,770, U.S. Pat. No. 4,683,335, U.S. Pat. No. 4,316,841, U.S. Pat. No. 4,463,193, U.S. Pat. No. 4,503,253, U.S. Pat. No. 4,560,798 and U.S. Pat. No. 4,578,517.

Suitable conventional phosphorus-containing substances which can be employed as performance moderators in this invention include acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorous acid compounds and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous acids and phosphoric acids, alkali metal monosalts of phosphoric acid, the thioanalogs of the foregoing, and mixtures of any of the above.

For purposes of this invention, the phosphorus-containing substances used as promoters and performance moderators herein should only be employed in amounts sufficient so as to not adversely affect HEDETA product selectivity. While not wishing to be bound to any particular theory, it is believed that phosphorus-containing substances are catalytically selective for the reaction of HEDETA and an alkyleneamine such as EDA to higher polyalkylene polyamines. Therefore, the amount of a phosphorus-containing substance used as a promoter or performance moderator herein is considered important to achieving amines products having a high yield weight percent of L-TEPA and HEDETA.

The amount of the performance moderator of the mineral acid type used with the condensation catalyst of the invention is not narrowly critical. Generally, the amount does not exceed 25 weight percent of the weight of the catalyst. As a rule, it is desirable to use at least 0.01 weight percent of the weight of the catalyst. Preferably, the amount of performance moderator will range from about 0.2 to about 10 weight percent of the weight of the catalyst. Most preferably, the amount of performance moderator will range from about 0.5 to about 5 weight percent of the weight of the catalyst.

The amount of performance moderator other than the mineral acid type used with the condensation catalyst is not narrowly critical. Generally, the amount does not exceed 90 weight percent of the weight of the catalyst. The amount of performance moderator can range from about 0 to about 90 or greater weight percent of the weight of the catalyst, preferably from about 0 to about 75 weight percent of the weight of the catalyst, and more preferably from about 0 to about 50 weight percent of the weight of the catalyst. Most preferably, the amount of performance moderator will range from about 0.5 to about 25 weight percent of the weight of the catalyst.

The performance moderator can be provided to the condensation catalyst by conventional procedures known in the art. For example, the performance moderator can be provided to the catalyst by impregnating particles or monolithic structures comprising the catalyst with liquid comprising the performance moderator. This is a well known procedure in the art for incorporating additives to a solid support material. The condensation catalyst of the invention may be utilized as solid powders or as fused, bonded or compressed solid pellets, or larger structures in association with the one or more metal oxides, or as coated, fused, bonded or compressed solid pellets, or larger structures, composited with one or more support materials, in association with one or more metal oxides. These solid structures may be treated with the performance moderator by mixing a liquid body of the performance moderator with the solid structure. For example, the condensation catalyst solids may be slurried in the performance moderator, drained, washed and suctioned to remove excess performance moderator and then dried with heat to remove any volatiles accompanying the performance moderator. The drying temperature chosen will depend on the nature of the volatiles to be removed. Usually, the time/temperature for effecting drying will be below the conditions for effecting dehydration to remove bound water from the metal oxide in association with the condensation catalyst. Normally the drying temperature will be greater than about 120° C. and below about 600° C. depending on the thermal stability of the catalyst or the fusion temperature of the particular phosphate specie used if any. The drying time will generally go down as the drying temperature rises and vice versus, and may extend from 5 seconds to about 24 hours.

Alternatively, the performance moderator can be provided to the condensation catalyst at the time of preparing the catalyst in association with one or more metal oxides. For example, one or more metal oxides may be condensed from their respective hydrolyzable monomers to the desired oxides to form oxide powders which can thereafter be blended and compressed with the catalyst to form pellets and larger structures of the metal oxide-containing condensation catalyst of this invention. The one or more metal oxides which can be used in association with the condensation catalyst in accordance with this invention can be provided from metal salts which can be heated to form the metal oxide. It is appreciated that the performance moderator can be incorporated into the molecular bonding configuration of the metal oxide-containing condensation catalyst by conventional procedures known in the art.

The condensation catalysts in association with one or more metal oxides prior to the optional treatment of the performance moderator may be prepared in a wide variety of ways. For example, one or more metal oxides may be provided as a partial condensate on a support, such as a silica or alpha, beta or gamma alumina, silicon carbide, and the like, and then condensed by heating to effect polymerization to the desired oxide form. The metal oxide(s) may be condensed from hydrolyzable monomers to the desired oxide, indeed, to form an oxide powder which can thereafter be compressed in the presence of a condensation catalyst to form pellets and larger structures of the metal oxide-containing condensation catalyst of the invention. A blend of the powder and condensation catalyst can be made into a shapeable paste which can be extruded and cut into pellets according to conventional procedures. The extrudate may thereafter be fired to cure the condensation catalyst and fix the structure. The cut extrudate may be blended with a support material such as those characterized above, and the blend fired to fuse the metal oxide-containing catalyst to the support.

In a preferred embodiment of this invention, a high surface area silica, germania, titania or zirconia can be slurried with an aqueous solution of ammonium metatungstate or sillicotungstic acid, extruded, and calcined at a temperature of about 400° C.

A preferred catalyst structure comprises a Group VIB and/or IVB metal oxide having a surface area of at least about 140 m² /gm which may or may not be bonded to a support material. The term "support," as used herein and in the claims, means a solid structure which does not adversely affect the catalytic properties of the catalyst and is at least as stable as the catalyst to the reaction medium. The support can function as an amine condensation catalyst independent of the condensation catalyst used herein, although it may have lower catalytic activity to the reaction. The support may act in concert with the catalyst to moderate the reaction. Some supports may contribute to the selectivity of the reaction. The catalyst structure can comprise from about 2 to about 60 percent by weight or greater of the support, more preferably from about 10 to about 50 percent by weight of the support, the remainder being the weight of the metal oxide(s) and condensation catalyst. Included in the weight of the support is the weight of any binding agent such as phosphates, sulfates, silicates, fluorides, and the like, and any other additive provided to stabilize or otherwise help in the manufacture of the catalyst. The support may be particles as large or larger than the catalyst component and "glued" to the condensation catalyst and/or metal oxide by virtue of a binding medium.

The support may constitute a separate phase in the process of extruding the catalytic structure. In this embodiment, the support forming material, preferably as a paste is blended with a paste of the condensation catalyst and one or more metal oxides or a partial condensate thereof. The paste may comprise the oxide forms of the support and the condensation catalyst, each blended with water, and/or binding agents. The extrudate of the blend is passed through a multiorificed die and chopped into pellets of the desired sizes. The particles may be doughnut shaped, spherical, and the like. Then the particles are calcined to dry them and complete any condensation reaction in the support and/or the metal oxide-containing condensation catalyst.

The use of supports for the condensation catalyst provides a number of significant advantages. It has been determined that some of the condensation catalysts are not as stable in the amines reaction media when utilized over an extended period of time. When the reaction is effected as a batch reaction, this matter is not a problem. However, when the reaction is effected with the condensation catalyst as part of a fixed bed in a tubular reactor, the preferred procedure for carrying out the invention, it is desirable to have the catalyst be more stable. When the condensation catalyst is combined with the support, it has greater stability for the reaction medium, and therefore, it is better able to be used in a fixed bed of a continuous reactor. The supported catalysts suffer only minimally from the leaching problems that the catalyst per se may have or the problems that are associated with certain conventional catalysts, such as acidic phosphorus compounds on silica.

The reactants used in the condensation process of the invention may be ammonia or organic compound containing --NH-- and any compound possessing an alcoholic hydroxyl group, subject to the following: the intramolecular condensation of an amino compound produces an amine having a lower molecular weight, and the intermolecular condensation of an amino compound with one or more of another amino compound or a compound containing an alcoholic hydroxyl group produces an amine having a lower, same or higher molecular weight than the reactants.

Illustrative of suitable reactants in effecting the overall process of the invention, include by way of example:

Ammonia

MEA--monoethanolamine

DEA--diethanolamine

DiHEED--dihydroxyethylethylenediamine

EDA--ethylenediamine

MeEDA--methylethylenediamine

EtEDA--ethylethylenediamine

AEEA-- N-(2-aminoethyl)ethanolamine

HEP-- N-(2-hydroxyethyl)piperazine

DETA--diethylenetriamine

HEDETA--hydroxyethyldiethylenetriamine

HETETA--hydroxyethyltriethylenetetramine

HETEPA--hydroxyethyltetraethylenepentamine

AEP--N-(2-aminoethyl)piperazine

PEHA--pentaethylenehexamine

PEHA Isomers

HEHA--hexaethylenepentamine

HEHA Isomers

HEOA--heptaethyleneoctamine

HEOA Isomers

HPA--higher polyalkylene polyamines

HPA Isomers

TETA Isomers (TETA's):

TAEA--trisaminoethylamine

TETA--triethylenetetramine

DPE--dipiperazinoethane

DAEP--diaminoethylpiperazine

PEEDA--piperazinoethylethylenediamine

TEPA--Isomers (TEPA's):

AETAEA--aminoethyltrisaminoethylamine

TEPA--tetraethylenepentamine

AEDPE--aminoethyldipiperazinoethane

AEDAEP--aminoethyldiaminoethylpiperazine

AEPEEDA--aminoethylpiperazinoethylethylenediamine

iAEPEEDA--isoaminoethylpiperazinoethylethylenediamine

BPEA--bispiperazinoethylamine

The foregoing also can represent the products of the reaction. For example, ammonia and MEA are frequently employed to produce EDA along with a variety of other amines, most of which are set forth above. Further, alkylene oxides such as ethylene oxide can be employed with ammonia and a variety of other amines to produce polyalkylene polyamines in accordance with this invention.

Glycol compounds can also be employed in the preparation of amines. Glycol compounds embrace diols and polyols. Illustrative of glycol compounds include alkylene glycols such as ethylene glycol.

The feed space velocity, feed mole ratio and reaction temperature and pressure are not narrowly critical and can vary over a wide range. The selection of these operating variables is dependent on desired conversions and product selectivity.

In particular, when DEA and EDA are employed as reactants in the process of this invention, an increase in DEA space velocity or EDA/DEA feed mole ratio will decrease conversion, while an increase in temperature will increase conversion. Typically, it is desired to operate at a high enough pressure to maintain the reactants primarily in the liquid phase. At a particular DEA space velocity, EDA/DEA feed mole ratio and temperature, the conversation will generally decrease if the pressure is lowered until the flow changes from liquid to vapor.

Lower reaction temperatures generally provide higher selectivity to desired products. As the EDA/DEA feed mole ratio increases, the selectivity to desired products increases. The EDA/DEA feed mole ratio may be used to adjust the relative amounts of L-TEPA and HEDETA. As the EDA/DEA feed mole ratio is increased, the L-TEPA to HEDETA weight ratio increases.

The process may be effected in the liquid or vapor or supercritical liquid states or mixtures thereof though the actual reaction is believed to occur on the catalyst's solid surface in the absorbed state. In this context, the vapor phase reaction is intended to refer to the general vapor state of the reactants. Though the reaction conditions may range from subatmospheric to superatmospheric conditions, it is desirable to run the reaction from about 50 psig to about 3,000 psig, preferably from about 200 psig to about 2,000 psig.

The temperature of the reaction may be as low as about 125° C. to about 400° C. Preferably, the reaction temperature ranges from about 150° C. to about 350° C., and most preferably from about 225° C. to about 325° C.

The reaction may be effected by the incremental addition of one of the reactants to the other or by the joint addition of the reactants to the catalyst. The preferred process effects the reaction in a continuous manner over a fixed bed of the condensation catalyst in a tubular reactor. However, the reaction may be carried out by slurrying the catalyst in the reactants or in a batch mode in an autoclave. An inert such as nitrogen, methane, hydrogen and the like can be used in the reaction process.

The process of the invention provides the ability to selectively generate the manufacture of desirable L-TEPA and HEDETA without generating large amounts of cyclic alkyleneamine products such as AEP and HEP. The alkyleneamines producers composition of this invention has a L-TEPA+ HEDETA to AEP weight ratio of greater than about 2.0 and a HEDETA to L-TEPA weight ratio of less than about 10.0.

This invention is further illustrated by certain of the following examples:

EXAMPLES

In the examples set forth in the tables below, the catalyst of choice was placed in a tubular reactor having an outside diameter of 1 inch and an overall length of 30 inches. The catalyst portion of the reactor comprised a length of 24 inches, capable of accommodating 150 cubic centimeters of catalyst. The reactor was made of 316 stainless steel.

For each of the examples, the tubular reaction system was brought to the designated conditions. The DEA and EDA were premixed to the appropriate feed mole ratio and then pressure fed to the system. The liquid feed was then mixed with nitrogen (if used) and this mixture was passed to a preheater prior to entering the reaction zone.

The reaction mixture was passed through the reaction zone in a downflow fashion. The pressure in the reaction zone was controlled by a motor valve at the outlet of the reactor. After leaving the reaction zone, the pressure of the stream was reduced from that of the reaction zone to slightly above atmospheric. This stream was then passed through a trap where the nitrogen (if used) was separated from the condensables which were collected in a semi-batch fashion. The condensable sample, which contains unreacted DEA and EDA and the products of the reaction, was then analyzed for water by a Karl-Fisher procedure and for organics (amines) by capillary gas chromatography.

The catalysts employed are identified as follows:

    ______________________________________                                         Designation Composition   Physical Properties                                  ______________________________________                                         A           TiO.sub.2 (anatase)/                                                                         Particle size:                                                   WO.sub.3      1/16 inch cylindrical                                            TiO.sub.2 /WO.sub.3 wt.                                                                      extrudates.                                                      ratio = 80/20                                                      B           TiO.sub.2 (anatase)/                                                                         Particle size:                                                   WO.sub.3      1/8 inch cylindrical                                             TiO.sub.2 /WO.sub.3 wt.                                                                      extrudates;                                                      ratio = 80/20 Catalyst surface area:                                                         227.9 m.sup.2 /gm.                                   C           TiO.sub.2 (anatase)/                                                                         Particle size:                                                   WO.sub.3      1/16 inch cylindrical                                            TiO.sub.2 /WO.sub.3 wt.                                                                      extrudates;                                                      ratio = 80/20 Catalyst surface area:                                                         166.3 m.sup.2 /gm.                                   ______________________________________                                    

The catalysts and/or supports employed in the examples hereinafter were obtained from Norton Company, Akron, Ohio. Certain of the catalysts and/or supports were subsequently treated as follows:

Catalyst A preparation: Silicotungstic acid (18.0 grams) was dissolved in distilled water (45 milliliters) and an aliquot sufficient to wet the TiO₂ /WO₃ support (55 grams) was used. After wetting, the catalyst was calcined at a temperature of 350° C. for a period of 1 hour. The impregnation and calcination steps were repeated twice more to give the catalyst.

                                      TABLE I                                      __________________________________________________________________________     Example No.                                                                               1   2   3   4   5   6   7   8   9   10                              __________________________________________________________________________     Process Parameters                                                             Catalyst Type                                                                             A   A   A   A   A   A   A   A   A   A                               Catalyst Weight, gm.                                                                      50  50  50  50  50  50  50  50  50  50                              Temperature, °C.                                                                   269.6                                                                              280 274.4                                                                              285.3                                                                              289.8                                                                              295.5                                                                              279.5                                                                              284.7                                                                              266.3                                                                              269.9                           Pressure, psig                                                                            614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                           Time on Organics,                                                                         494.5                                                                              499 518.5                                                                              523 543 547 566.5                                                                              571 589.5                                                                              614.5                           hrs.                                                                           DEA SV,    2.43                                                                               3.21                                                                               2.13                                                                               2.52                                                                               2.01                                                                               3.14                                                                               2.40                                                                               2.61                                                                               3.45                                                                               2.52                            gmol/hr/kgcat                                                                  EDA/DEA    4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                            mole ratio                                                                     Crude Product                                                                  Composition, wt. %                                                             AEP        7.14                                                                               8.45                                                                               7.18                                                                               10.42                                                                              12.71                                                                              15.75                                                                              9.03                                                                               9.46                                                                               4.93                                                                               4.82                            HEDETA     61.88                                                                              58.00                                                                              64.98                                                                              52.05                                                                              41.00                                                                              31.04                                                                              58.45                                                                              54.77                                                                              74.23                                                                              75.57                           L-TEPA     11.35                                                                              13.04                                                                              11.98                                                                              15.24                                                                              16.90                                                                              18.51                                                                              12.89                                                                              14.82                                                                              8.36                                                                               8.47                            Others     19.64                                                                              20.51                                                                              15.86                                                                              22.29                                                                              29.38                                                                              34.70                                                                              19.63                                                                              20.95                                                                              12.48                                                                              11.14                           Calculated Results                                                             DEA Conversion, %                                                                         41.26                                                                              51.90                                                                              47.05                                                                              60.93                                                                              74.52                                                                              83.31                                                                              56.92                                                                              63.94                                                                              38.94                                                                              35.97                           EDA Conversion, %                                                                         5.31                                                                               8.86                                                                               9.00                                                                               12.01                                                                              12.42                                                                              13.61                                                                              10.98                                                                              12.68                                                                              5.26                                                                               5.42                            HEDETA/AEP,                                                                               8.67                                                                               6.86                                                                               9.05                                                                               5.00                                                                               3.23                                                                               1.97                                                                               6.47                                                                               5.79                                                                               15.06                                                                              15.68                           weight ratio                                                                   HEDETA +   10.25                                                                              8.41                                                                               10.72                                                                              6.46                                                                               4.56                                                                               3.15                                                                               7.90                                                                               7.36                                                                               16.75                                                                              17.44                           L-TEPA/AEP,                                                                    weight ratio                                                                   HEDETA/L-TEPA,                                                                            5.45                                                                               4.45                                                                               5.42                                                                               3.41                                                                               2.43                                                                               1.68                                                                               4.53                                                                               3.70                                                                               8.88                                                                               8.93                            weight ratio                                                                   __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________     Example No.                                                                               11  12  13  14  15  16  17  18  19  20                              __________________________________________________________________________     Process Parameters                                                             Catalyst Type                                                                             B   B   B   B   B   B   B   B   B   B                               Catalyst Weight, gm.                                                                      50  50  50  50  50  50  50  50  50  50                              Temperature, °C.                                                                   269.6                                                                              280 274.4                                                                              285.3                                                                              289.8                                                                              295.5                                                                              279.5                                                                              284.7                                                                              266.3                                                                              269.9                           Pressure, psig                                                                            614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                           Time on Organics,                                                                         494.5                                                                              499 518.5                                                                              523 543 547 566.5                                                                              571 589.5                                                                              614.5                           hrs.                                                                           DEA SV,    2.50                                                                               3.03                                                                               2.09                                                                               2.95                                                                               2.23                                                                               3.23                                                                               2.34                                                                               3.31                                                                               2.63                                                                               2.88                            gmol/hr/kgcat                                                                  EDA/DEA    4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                            mole ratio                                                                     Crude Product                                                                  Composition, wt. %                                                             AEP        7.54                                                                               9.94                                                                               8.61                                                                               11.93                                                                              16.58                                                                              19.02                                                                              11.17                                                                              10.93                                                                              6.72                                                                               6.51                            HEDETA     65.92                                                                              55.04                                                                              62.84                                                                              48.07                                                                              30.07                                                                              24.99                                                                              51.26                                                                              49.51                                                                              70.52                                                                              69.95                           L-TEPA     13.06                                                                              17.02                                                                              15.29                                                                              19.72                                                                              26.42                                                                              23.89                                                                              17.97                                                                              19.10                                                                              11.83                                                                              12.30                           Others     13.48                                                                              18.00                                                                              13.26                                                                              20.28                                                                              26.93                                                                              32.09                                                                              19.60                                                                              20.45                                                                              10.93                                                                              11.24                           Calculated Results                                                             DEA Conversion, %                                                                         52.87                                                                              65.35                                                                              57.72                                                                              77.11                                                                              88.18                                                                              90.86                                                                              72.97                                                                              74.15                                                                              51.51                                                                              51.96                           EDA Conversion, %                                                                         6.46                                                                               11.91                                                                              9.85                                                                               12.31                                                                              13.89                                                                              12.68                                                                              12.81                                                                              13.78                                                                              8.48                                                                               9.03                            HEDETA/AEP,                                                                               8.75                                                                               5.54                                                                               7.30                                                                               4.03                                                                               1.81                                                                               1.31                                                                               4.59                                                                               4.53                                                                               10.50                                                                              10.75                           weight ratio                                                                   HEDETA +   10.48                                                                              7.25                                                                               9.07                                                                               5.68                                                                               3.41                                                                               2.57                                                                               6.20                                                                               6.28                                                                               12.26                                                                              12.64                           L-TEPA/AEP,                                                                    weight ratio                                                                   HEDETA/L-TEPA,                                                                            5.05                                                                               3.23                                                                               4.11                                                                               2.44                                                                               1.14                                                                               1.05                                                                               2.85                                                                               2.59                                                                               5.96                                                                               5.69                            weight ratio                                                                   __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     Example No.                                                                               21  22  23  24  25  26  27  28  29  30                              __________________________________________________________________________     Process Parameters                                                             Catalyst Type                                                                             C   C   C   C   C   C   C   C   C   C                               Catalyst Weight, gm.                                                                      50  50  50  50  50  50  50  50  50  50                              Temperature, °C.                                                                   269.6                                                                              280 274.4                                                                              285.3                                                                              289.8                                                                              295.5                                                                              279.5                                                                              284.7                                                                              266.3                                                                              269.9                           Pressure, psig                                                                            614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                                                                              614.7                           Time on Organics,                                                                         494.5                                                                              499 518.5                                                                              523 543 547 566.5                                                                              571 589.5                                                                              614.5                           hrs.                                                                           DEA SV,    2.40                                                                               2.94                                                                               2.04                                                                               2.79                                                                               2.27                                                                               2.69                                                                               2.22                                                                               2.57                                                                               2.35                                                                               2.76                            gmol/hr/kgcat                                                                  EDA/DEA    4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                                                                               4.00                            mole ratio                                                                     Crude Product                                                                  Composition, wt. %                                                             AEP        6.41                                                                               8.18                                                                               7.00                                                                               10.31                                                                              12.76                                                                              16.86                                                                              8.86                                                                               9.49                                                                               5.88                                                                               5.92                            HEDETA     66.47                                                                              61.14                                                                              66.46                                                                              48.36                                                                              41.83                                                                              24.53                                                                              56.24                                                                              50.98                                                                              71.80                                                                              70.90                           L-TEPA     10.52                                                                              14.00                                                                              11.84                                                                              16.88                                                                              19.64                                                                              25.93                                                                              15.25                                                                              17.32                                                                              10.12                                                                              10.12                           Others     16.60                                                                              16.68                                                                              14.71                                                                              24.46                                                                              25.76                                                                              32.67                                                                              19.65                                                                              22.22                                                                              12.20                                                                              13.06                           Calculated Results                                                             DEA Conversion, %                                                                         48.84                                                                              61.29                                                                              52.42                                                                              75.05                                                                              81.22                                                                              91.80                                                                              66.48                                                                              73.49                                                                              47.55                                                                              48.25                           EDA Conversion, %                                                                         5.53                                                                               8.38                                                                               7.40                                                                               13.04                                                                              10.65                                                                              12.39                                                                              13.32                                                                              13.88                                                                              7.79                                                                               8.27                            HEDETA/AEP,                                                                               10.37                                                                              7.48                                                                               9.50                                                                               4.69                                                                               3.28                                                                               1.45                                                                               6.35                                                                               5.37                                                                               12.22                                                                              11.98                           weight ratio                                                                   HEDETA +   12.01                                                                              9.19                                                                               11.19                                                                              6.33                                                                               4.82                                                                               2.99                                                                               8.07                                                                               7.20                                                                               13.94                                                                              13.69                           L-TEPA/AEP,                                                                    weight ratio                                                                   HEDETA/L-TEPA,                                                                            6.32                                                                               4.37                                                                               5.62                                                                               2.87                                                                               2.13                                                                               0.95                                                                               3.69                                                                               2.94                                                                               7.09                                                                               7.00                            weight ratio                                                                   __________________________________________________________________________

Although the invention has been illustrated by certain of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof. 

We claim:
 1. A process for making linear tetraethylenepentamine and hydroxyethyldiethylenetriamine comprising condensing, in the absence of hydrogen as a reactant, ethylenediamine and diethanolamine under condensation conditions including the presence of a catalytically effective amount of a condensation catalyst consisting essentially of a metatungstate and one or more Group IVB metal oxides, wherein the ethylenediamine to diethanolamine feed mole ratio is sufficient to provide under condensation conditions an amines product, based on 100 percent of the weight of the amines product and exclusive of any water and/or ammonia and/or feed present,(a) greater than about 8.0 weight percent of L-TEPA, (b) greater than about 10.0 weight percent of HEDETA, (c) less than about 30.0 weight percent of AEP, (d) less than about 35.0 weight percent of others, (e) a HEDETA to L-TEPA weight ratio of less than about 10.0, and (f) a L-TEPA+HEDETA to AEP weight ratio of greater than about 2.0.
 2. The process of claim 1 wherein the Group IVB metal oxide comprises a high surface area titanium oxide or zirconium oxide.
 3. The process of claim 1 wherein the condensation catalyst has a surface area greater than about 70 cm² /gm.
 4. The process of claim 2 wherein the titanium oxide comprises titanium dioxide and the zirconium oxide comprises zirconium dioxide.
 5. The process of claim 2 wherein the condensation catalyst has a surface area greater than about 140 m² /gm.
 6. The process of claim 2 wherein the condensation catalyst has a surface area greater than about 70 m² /gm.
 7. The process of claim 1 wherein the Group IVB metal oxide comprises from about 25 weight percent to about 90 weight percent of the weight of the catalyst.
 8. The process of claim 1 wherein the Group IVB metal oxide comprises from about 50 weight percent to about 90 weight percent of the weight of the catalyst.
 9. The process of claim 1 wherein the Group IVB metal oxide comprises from about 75 weight percent to about 90 weight percent of the weight of the catalyst.
 10. The process of claim 1 wherein the condensation catalyst is associated with a support material.
 11. The process of claim 10 wherein the support comprises an alumina material or an alumina-silica material.
 12. The process of claim 10 wherein the support comprises a silica material or a silica-alumina material.
 13. The process of claim 10 wherein the support comprises from about 2 to about 50 percent by weight of the condensation catalyst.
 14. The process of claim 1 wherein the ethylenediamine and diethanolamine are condensed in the presence of ammonia.
 15. The process of claim 1 wherein the amines product has a L-TEPA yield weight percent of greater than about 12.0 and an HEDETA yield weight percent of greater than about 20.0, based on 100 percent of the weight of the product and exclusive of any water and/or ammonia and/or feed present.
 16. The process of claim 1 which is conducted at a temperature of from about 125° C. to about 400° C.
 17. The process of claim 1 which is conducted at a pressure of from about 50 psig to about 3000 psig.
 18. The process of claim 1 which is effected in the liquid or vapor or supercritical liquid states. 